N-allyl derivatives of acrylic esteramides and polymers thereof



Patented no. 4,1949 2,458,423

' UNITED STATES PATENT OFFICE 2.45am

N-ALLYL DERIVATIVES OF ACRYLIC ESTER- AMIDES AND POLYMERS THEREOF Delbert D. Reynolds and John B. Van Campen, Rochester, N. Y., auignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey I No Drawing. Application November 22, 1947,

7 Claims. (Cl. 280-88) This invention relates to a new roup of acrylic preparing the same. Other objects will become ester-amides containing an allyl group, polymers apparent hereinafter.

thereof, and to processes for their preparation. In accordance with the invention, the new The new N-allyl acrylic ester-amides oi the inacrylic ester-amides are prepared by esterifying .jention can be represented by the structural ior- N-allyl lactamide or N- s-substituted allyl) lacmula: tamides with acrylic or o-substituted acrylic an- -0 ov om=o-i':-o-on-8-Nnom-0=om general mmulai I Hl=-Ol R H: l 10 I in which R represents an atom of hydrogen, a halogen m schlorine o bro e) a mac wherein Y represents hydrogen, a halogen atom, group, a saturated alkyl group (e. 8. methyl. a cyano group, a saturated alkyl group, an aryl hy propyl. is pr pyl, butyhisobutyhsemb iyli' group, an srslkyl group, an alkoxy or aryloxy tert. butyl, etc.), an aryl group (e. g. phenyl, group.acycloalkyl group, an acyl group, anacylnaphthyl, tolyl, xylyl, etc.), an aralkyl group oxy group,aheterocyclic group,acarboxyl group,

hydrides, or with acrylyl chlorides having the (e. s. ben y p e ylet yl, etc.), an alkoxr or a carbalkoxy group, an amino group or an acyl- 811710 3 group (e. g. methoxy, ethoxy, prop namido group, as previously defined. Where the isopropoxy, butoxy, phenoxy, etc.), a cycioalkyl acid chlorides are employed as the esterifying group (e. g. cyclopropyl, cyclobutyl, cyciohexyl. 3 agents, the reactioniscarriedout advantageously etc. an acyl r u sa tyl. p p buata temperaturemot exceeding 40 0., in an inert tyryl, etc.), an acyloxy group (e. g. acetoxy, prosolvent medium such as anhydrous benzene, pionyloxy, butyryloxy, etc), a heterocyclic group methyl acetate, chloroform, dioxane, etc., and (e. g. piperidyl), a carboxyl group, a carbalkoxy in the presence of fan acid-binding agent, for exgroup (e. g.-carbmethoxy, carbethoxy, etc.), an ample, anhydrous sodium carbonate, and a deamino group (e. g. dimethylamino, diphenylamihydrating agent,'ior example, anhydrous calcium no, methylphenylamino. etc.), a diacylamido sulfate. This process is described and claimed in group (e. g. phthalin ido, etc.), and similar copending application, Serial No. 787,605, filed groups, and R1 represents hydrogen, a halogen o of even date herewith, in thenames of Delbert (e. g. chlorine or bromine) or a saturated alkyl 3 D. Reynolds and William O. Kenyon. Where the group (e. g. methyl, ethyl, propyl, isopropyl, butyl. acid anhydrides are employed as the esterifying etc.). The above deilned new allyl groups conagents, the reaction can be carriedout advantataining ester-amides are non-resinous, crystalgeously in the presence of a polymerization inline compounds which have distinct melting hibitor such as a copper salt and an organic base points and physical properties, and are capable such as pyridine.

of isolation in substantially pure state as shown Suitable lactamides tor the preparation of the in the examples which-Iflfollow, 'I'hey are soluble new ester-amides include N-allyl lactamide, N-pinmost or the common {organic solvents suchas methallyl lactamide, N-p-ethallyl lactamide. N- benzene, chloroform,- 'mixtu'resof diethyl'ether pepropallyllactamlde,N-p-lsopropallyl la t miqe,

and petroleum ether, acetone, .dioxane, etc. The N-p-butallyl t m N-p-sec, butallyl new ester-amides are also valuable intermediates tamide, N-p-isohutallyl lactamide, N-p-tert. bu-

for the preparation of other useful chemical comtallyl lactamide, N-p-chloro iactamide, etc. pounds. They are also excellent. v I amides may be prepared by reacting alkyl agents in compositions for impregnatin'g'pape and textile fabrics, being cap'able'oilpolymelfilia tion to insoluble resins in the particular r, ethyl, lactate with ally or with an ally M'i'actic acid such as, for example, methyl l itinine isllbs tituted on the'beta-carbon atom with s0 impregnated or treated. In additionfthey a saturated lower alkyl compound such as, for a are polymerizable alone or conjointly with other example, p-methallylamine, p-ethallylamine, punsaturated compounds to products which have propallylamine, p-isopropallylamine, p-butallylsolubility characteristics associated with the amine, fl-sec. butallylamine, p-isobutallylamine, three dimensional type of resins. *p-tert. butallylamine, p-chloroallylamine, 'etc.

It is, accordingly, an object of the invention Ordinarily, the lactate is mixed together with an to provide a new group of acrylic ester-amides excess oi the allylamine, the mixture heated and which contain an allyl group, and polymers therethe lactamide product then isolated by fractional of. Another object is to provide a method for distillation. The above mentioned intermediate 3 beta-substituted allylamines may be made by the method described in U. S. Patent 2,072,015, issued February 23, 1937.

The polymerization of the new ester-amides alone or conjointly with one or more other polymerizable compounds is accelerated by heat, and by polymerization catalysts 'which are known to accelerate the polymerization of acrylic compounds. Exemplary of such catalysts are the organic peroxides (e. g. benzoyl peroxide, acetyl peroxide and lauroyl peroxide), hydrogen peroxide, perborates (e. g. alkali metal perborates) and persulfates (e. g. alkali metal persulfates). The polymerization can be efleoted in mass or in the presence of a diluent such as, for example, dioxane. However, the monomers can also be emulsified in a liquid in which they are insoluble (e. g. water) and the emulsion subjected to polymerization. The monomers can also be suspended in water using relatively poor dispersing agents such as starch, and polymerized in the form of granules. The monomers can also be copolymerized with one or more other ethylenic monomers having the general formulas:

wherein Y and/or Z are alkyl, aryl, aralkyl, alkoxyl, aryloxyl, aralkoxyl, halogeno, acylamido, sulfonamido, sulfamyl, acyloxyl, carbalkoxyl, carbamide, nitrile, aldehydo, heterocyclic, dialkylamino, acylimino, etc. Specific compounds coming within-the scope of the above formulas include among others 1,2-propylene, furylethylene, isobutylene, vinyl iormate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl thioacetate, virLvl benzoate, vinyl oxalate, isopropenyl acetate, methylene dimethyl malonate, divinyl formal, acrolein, a-methacrolein, vinyl chloride, vinyl bromide, isopropenyl chloride, vinylidene chloride, vinyl chloroacetate, vinyl trichloroacetate, vinyl isocyanate, isopropenyl isocyanate,. vinyl acetylene, vinyl urethane, vinyl methyl ketone, vinyl phenyl ketone, vinyl benzyl ketone, vinyl cyclohexyl ketone, vinyl furyl ketone, vinyl p-tolyl ketone, isopropenyl methyl ketone, vinyl methyl ether, vinyl butyl ether, divinyl ether, vinyl phenyl ether, isopropenyl methyl ether, vinyl sulfonamide, vinyl sulfonic acid, vinyl p-tolyl sulfoxlde, vinyl fl-naphthyl sulfone, vinyl p-tolyl sulfone, isopropenyl methyl sulfone, butadiene, isoprene, chloroprene, 2- acetoxy butadiene-1,3, N-vinyl acetamide, N- vinyl methylacetamide, N-vinyl phenylacetamide, N-vinyl ethylacetamide, N-vinyl methylforamide, N-vinyl acetanilide, N-vinyl p-tolyl acetamide, N-vinyl cyclohexylacetamide, N-vinyl N-methyl butyramide. N-vinyl pyrrole, N-vinyl pyrollidine, N-vinyl carbazole, vinyl pyridine, vinyl quinoline, styrene, a-methylstyrene, a-chlorostyrene, vinyl phenol, vinyl naphthalene, divinyl benzene, isopropenyl benzene, N-vinyl succinimide, N-vinyl tetrahydrophthalimide, N-vinyl .phthalimide, N- vinyl glutarimide, N-vinyl diglycolylimide, N-isopropenyl phthalimide, acrylonitrile, methacrylonitrile, a-methoxyacrylonitrile, a-acetoxyacrylonitrile, a-chloroacrylonitrile, a-phthalimidoacrylonitrile, a-phenoxyacrylonitrile; acrylic acid, methacrylic acid, m-chloroacrylic acid, methyl acrylate, methyl methacrylate, methyl ethacrylate, benzyl acrylate, allyl methacrylate, 3- ethoxyethyl acrylate, acrylamide, N-diacetyl acrylamide, N-ethyl acrylamide, N-diethyl acryl- The preferred copolymers of the invention are 7 obtained with starting polymerization mixtures having from 0.2 to 99.8 parts by weight of the new N-allyl acrylic ester-amide and from 99.8 to 0.2 parts by weight of one or more of the other above mentioned unsaturated organic compounds.

The following examples will serve to illustrate our new ester-amides, polymers thereof, and the process 01'- their preparation.

Example 1.N-allyl lactamide A mixture 01 236 gms. of ethyl lactate and 348 gms. oi allylamine was heated on a steam bath for a period oi 30 hours. The excess allylamine and other low-boiling by-products were distilled from the mixture at a pressure of 15 to 20 mm. The residue was finally distilled at 116C. at 1 mm. pressure. Analysis for nitrogen indicated that the clear, colorless, mobile liquid thus obtained was practically pure N-allyl lactamide. This compound is described and claimed in copending application, Serial No. 787,604, filed of even date herewith, in the names of W. 0. Kenyon and J. H. Van Campen.

Example 2.-N-allyl a-methacrylory propionamide 258 gms. of N-allyl 'lactamide, 400 gms. of methacrylic anhydride, 15 cc. of anhydrous pyridine and 5 gms. of copper carbonate were mixed together and heated on a steam bath for a period of 18 hours. To this mixture was added 500 cc. of benzene, and the resulting solution washed with an aqueous sodium carbonate solution and then with water. The benzene layer was dried over anhydrous magnesium sulfate and the henzene evaporated off by means of a stream of dry air blowing on the surface. The product, N-allyl a-methacryloxy propionamide, crystallized out of a the solution, and after recrystallization from a low boiling hydrocarbon solvent had a melting point of 64 C. Analysis for nitrogen gave 7.07 per cent by weight as compared with calculated theory of 7.1 per cent.

In place of the N-allyl lactamide in the above example, there was substituted 286 gms. of N-p-methallyl lactamide to give the compound N-p-methallyl a-methacryloxy propionamide.

Example 3.N-allyl a-acrylomy propionamide A mixture of 1 liter of anhydrous chloroform, 200 gms. of anhydrous sodium carbonate, 400 gms. of anhydrous calcium sulfate and 109 gms. of allyl lactamide was stirred for one hour. The mixture was cooled to 10 C. and gms. of acrylyl chloride added. The temperature of the reaction mixture was allowed to rise to room temperature, then warmed to 30 C. and stirred at this temperature for an additional five hours. There was added 50 cc. of anhydrous pyridine,

followed by 12 more hours of stirring. The re-- action mixture was filtered and the filtrate evaporated to a thick syrup at room temperature. A

mixture of diethyl ether and petroleum ether was stirred into the syrup, until the mixture became homogenous. Upon removal of this solvent mixture, the product, N-allyl a-acryloxy propionamide, separated out of solution in the form of crystals.

Example -4.Poly-N-allyl a-methacrylomy propionamide 5 gms. of N-allyl a-methacryloxy propionamide were mixed with 50 gms. of benzoyl peroxide and warmed on a steam bath. In less than minutes, there had formed a clear, hard polymer. This polymer was insoluble in all common organic solvents.

Example 5.Poly-N-allyl a-acryloscy propz'onamide 10 gms. of N-allyl a-acryloxy propionamide were mixed with cc. of anhydrous dioxane and 0.1 gm. of benzoyl peroxide added. After warming for a period of about one-half hour on a steam bath, a white, insoluble polymer had precipitated. This polymer was washed with methanol and dried. It was insoluble in all common organic solvents.

Example 6.-C'0polymer of N-allyl a-methacryloxy propionamide and methyl methacrylate A mixture of 1 gm. of N-allyl a-methacryloxy propionamide, 19 gms. of methyl methacrylate and 0.1 gm. of benzoyl peroxide was placed into a pyrex tube, which was sealed and put into a 60 C. water bath. The copolymer obtained was a clear, hard,'bubbly mass and was insoluble in organic solvents.

Example 7.Copolymer of N-allyl a-methacrylomy propzonamide, isopropenyl acetate and diethyl fumarate A mixture of 1 gm..of N-allyl a-methacryloxy propionamide, 7 gms. of isopropenyl acetate, 12 gms. of diethyl fumarate and 0.1 gm. of benzoyl peroxide was sealed in a pyrex glass tube and placed in a 60, C. water bath. A clear, hard copolymer was obtained. This copolymer was insoluble in acetone and other organic solvents.

In place of the N-allyl a-methacryloxy propionamide in the above example, there was substituted 1 gm. of N-p-methallyl a-methacryloxy propionamid-e to give a similar clear, hard and insoluble copolymer.

Example 10.C0pol1jmer of N-allyl a-acryloxy propionamide and vinyl acetate A mixture of 18.3 gms. of N-allyl a-acryloxy propionamide, 8.6 gms. of vinyl acetate and 0.3 gm. of benzoyl peroxide was heated in a sealed tube at C. for a period of 2 days.

A clear,

soft, but firm resin was obtained which was insoluble in all common organic solvents.

Other examples of our new copolymeric compounds prepared in similar manner as the preceding examples are illustrated in the following 99 Vinyl acetate Hard, crumbly mid insoluble in orgnnir solvents.

2 98 Vinyl acetate Do. 5 95 Vinyl acetate Do.

99 Styrene Hard and insoluble in 1,4-dioxane. 98 Styrene Do. 95 Styrene Do.

Clear, soft and insol;:-

Example 8.--Copolymer of N-allyl a-acryloxy propz'onamz'de and styrene Example 9.C'opolymer of N-allyl a-acryloxy propionamz'de and methyl acrylate A mixture of 18.3 gms. of N-allyl a-acryloxy propionamide, 8.6 gms. of methyl acrylate and 0.3

gm. of benzoyl peroxide was heated in a sealed tube at 50 C., for a period of 2 days. The clear, hard polymer thus obtained was insoluble in all common organic solvents.

99 Diethyl fumarate..

98 Diethyl tamer-ate...

Diethyl fumaratc.

his in organic sot vents.

Clear, rubbery and insoluble in orgam'isolvents.

Hazy, rubbery and in soluble in Ol'gflfiii" solvents.

36.5 Isopropenyl'acetate,

Hard, clear and if;

62.5 Diethylfumarate. soluble in organ solvents. 2 36 Isopropenyl acetate, Do.

62 Diethyl fumarate. 5 35 Isopropenyl acetate, Do.

60 Diethyl fumarate.

36.5 Vinyl acetate, 62.5

Hard, clear and insol- Diethyliumarate. uble in organic solvents. 2 36 Vinyl acetate, 62 Do.

Diethyl fumaratc. 5 35 Vinyl acetate, 60 Do.

Diethyl furnamte.

When completely polymerized, an the homopolymers and copolymers made from our new ester-amides are insoluble in all the common organic solvents, indicating thereby a definite crosslinking property. Due to the presence, however. of the lactic acid group interposed between the unsaturated end groups of the ester-amide molecule, the cross-links between the resin chains are longer and allow more movement between the polymer molecules so cross-linked. As a consequence, the new polymers are less compact and dense, and accordingly have improved physical properties over polymers not containing the lactic acid group. This permits of wider application of these polymers. For example, any of the monomeric ester-amides or mixtures of the monomeric ester-amides with one or more of the other monomeric unsaturated compounds, above mentioned. may be employed in solution in an organic solvent or in suspension in a carrier medium such as water, and containing filling materials and other substances such as a polymerization catalyst, to impregnate or coat paper, textile materials such as threads, fibers, fabrics of cellulose, cellulose esters and synthetic textile materials, etc., followed by heating the impregnated or coated material to polymerize the unsaturated constituents thus absorbed or coated into insoluble forms. The materials so treated are rendered waterproof and organic solvent proof.

We claim: 1. A- compound having'the general structural formula group, an aralkyl group, an alkoxy group, an.

aryloxy group, a cycloalkyl group, a carboxylic acid acyl group. a carboxylic acid acyloxy group, a piperidyl group, a carboxyl group, a carbalkoxy group and an amino group, and R1 represents a member selected from the group consisting of an atom of hydrogen, a halogen atom and an alkyl group.

2. N-allyi a-methacryloxy propionamide.

3. N-allyl a-aeryloxy propionamide.

4. N p methallyl a -'methacry1oxy propionamide.

5. A polymer of a compound having the general structural formula:

wherein R represents a member selected from the group consisting 01 an atom of hydrogen, a halogen atom, a cyano group, an alkyl group, an

aryl-group, an aralkyl group, an alkoxy group, an,

6. A copolymer of from 0.2 to 99.8 parts by weight of N-allyl a-methacryloxy propionamide and from 99.8 to 0.2 part'by weight of methyl methacrylate.

7. A copolymer of from 0.2 to 99.8 parts by weight oi N-allyl a-acryloxy propionamide and from 99.8 to 0.2 part by weight of styrene.

DELBERT D. REYNOLDS. JOHN H. VAN CAMPEN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,141,546 Strain Dec.'2'7, 1938 2,311,548

Jacobson et a1. Feb. 16, 1943 

